Apparatus for regeneration of acidic ionic liquid without addition of a hydrogenation catalyst

ABSTRACT

We provide a process for regenerating a spent acidic ionic liquid, comprising contacting the spent acidic ionic liquid with hydrogen and without an addition of a hydrogenation catalyst; wherein a conjunct polymer content is decreased in the spent acidic ionic liquid to produce regenerated acidic ionic liquid. We also provide a process for making an alkylate gasoline blending component, comprising: a) alkylating a mixture of isoparaffins and olefins using an acidic ionic liquid and an alkyl halide or a hydrogen halide, wherein a conjunct polymer accumulates in a spent acidic ionic liquid; and b) feeding the spent acidic ionic liquid and a hydrogen, and without an addition of a hydrogenation catalyst, to a regeneration reactor operated under selected hydrogenation conditions to produce a regenerated acidic ionic liquid that is used for the alkylating, wherein the conjunct polymer in the regenerated acidic ionic liquid is decreased by at least 50 wt %.

This application is a divisional of application Ser. No. 15/010,168,titled “REGENERATION OF ACIDIC IONIC LIQUID WITHOUT ADDITION OF AHYDROGENATION CATALYST”, published as US20170216827A1, filed on Jan. 29,2016, assigned to Art Unit 1734, herein incorporated in its entirety.

TECHNICAL FIELD

This application is directed to a process for regenerating a spentacidic ionic liquid without the addition of a hydrogenation catalyst.This application is also directed to a process for making an alkylategasoline blending component including feeding a spent acidic ionicliquid and hydrogen to a regeneration reactor, without the addition ofany solid hydrogenation catalyst to the regeneration reactor.

BACKGROUND

Improved processes are needed for regenerating spent acidic ionicliquids. Earlier processes have required significant quantities ofhydrogenation catalysts to perform the hydro-regeneration. Hydrogenationcatalysts need to be periodically replaced and/or regenerated, and theycan be costly to purchase, handle, and dispose of.

SUMMARY

This application provides a process for regenerating a spent acidicionic liquid, comprising contacting the spent acidic ionic liquid withhydrogen and without an addition of a hydrogenation catalyst; wherein acontent of a conjunct polymer is decreased in the spent acidic ionicliquid to produce a regenerated acidic ionic liquid.

This application also provides a process for making an alkylate gasolineblending component, comprising:

-   -   a. alkylating a mixture of one or more C₄-C₇ isoparaffins and        one or more C₂-C₆ olefins in a presence of an acidic ionic        liquid and an alkyl halide or a hydrogen halide, to produce the        alkylate gasoline blending component, wherein a conjunct polymer        is accumulated in a spent acidic ionic liquid;    -   b. feeding the spent acidic ionic liquid and a hydrogen, and        without the addition of a hydrogenation catalyst, to a        regeneration reactor operated under hydrogenation conditions        including a temperature from 100° C. to 350° C. and a pressure        from 50 to 5000 psig (445 to 34600 kpa), wherein a content of        the conjunct polymer is decreased by at least 50 wt % in the        spent acidic ionic liquid and the spent acidic ionic liquid        becomes a regenerated acidic ionic liquid that is used as a        catalyst for the alkylating.

The present invention may suitably comprise, consist of, or consistessentially of, the elements in the claims, as described herein.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic diagram of the experimental apparatus used inExamples 2 and 4-7 in this disclosure.

FIG. 2 is a graph of the moles of hydrogen consumed/g of ionic liquid,and conjunct polymer content, plotted vs. the reaction time from theExample 2 in this disclosure.

FIG. 3 is a graph of the moles of hydrogen consumed/g of ionic liquid,and conjunct polymer content, plotted vs. the reaction time from theExample 3 in this disclosure

FIG. 4 is a graph of the moles of hydrogen consumed/g of ionic liquid,and conjunct polymer content, plotted vs. the reaction time from the twosets of experiments described in Example 5 of this disclosure.

FIG. 5 is a graph of the moles of hydrogen consumed/g of ionic liquidvs. the reaction time in the three sets of experiments described inExample 7 of this disclosure.

FIG. 6 is a graph of the wt % conjunct polymer content vs. the reactiontime in the three sets of experiments described in Example 7 of thisdisclosure.

FIG. 7 is a schematic diagram of the experimental apparatus used inExample 8 in this disclosure.

FIG. 8 is a graph showing the impact of the mode of hydrogenintroduction on conjunct polymer content over time, and includes resultsfrom Example 2 and Example 8.

GLOSSARY

-   “Acidic ionic liquid” refers to materials consisting entirely of    ions, that can donate a proton or accept an electron pair in    reactions, and that are liquid below 100° C.-   “Spent” refers to a less active catalytic material that has been    contaminated during use, typically with conjunct polymer.-   “Addition” refers to a purposeful step of adding a different    material, e.g., a hydrogenation catalyst, to a vessel used for the    contacting.-   “Hydrogenation” refers to a chemical reaction between molecular    hydrogen (H₂) and another compound or element to reduce or saturate    organic compounds. For example, hydrogenation reduces double and    triple bonds in hydrocarbons.-   “Hydrogenation catalyst” refers to a metal-containing material that    catalyzes hydrogenation of organic compounds.-   “Periodic Table” refers to the version of the IUPAC Periodic Table    of the Elements dated Jun. 22, 2007, and the numbering scheme for    the Periodic Table Groups is as described in Chemical And    Engineering News, 63(5), 27 (1985).-   “Conjunct polymer” refers to poly-unsaturated cyclic, polycyclic,    and acyclic molecules formed by concurrent acid-catalyzed reactions    including, among others, polymerization, alkylation, cyclization,    and hydride transfer reactions. Conjunct polymers contain double and    conjugated double bonds in intricate structures containing a    combination of cyclic and acyclic skeletons. Examples of conjunct    polymers are described by Miron et al. (Journal of Chemical And    Engineering Data, 1963) and Pines (Pines, H., The Chemistry of    Catalytic Hydrocarbon Conversions, Wiley, 1981, p. 39ff).-   “Hydrocracking” refers to a process in which hydrogenation and    dehydrogenation accompanies the cracking/fragmentation of    hydrocarbons, e.g., converting heavier hydrocarbons into lighter    hydrocarbons, or converting aromatics and/or    cycloparaffins(naphthenes) into non-cyclic branched paraffins.-   “Noble metal” refers to a metal that is resistant to corrosion and    oxidation in moist air (unlike most base metals). Examples of noble    metals are ruthenium, rhodium, palladium, silver, osmium, iridium,    platinum, and gold.

DETAILED DESCRIPTION

Hydrogenation is known to be an effective method used to regeneratespent acidic ionic liquids, but the processes known previously allrequired the addition of a hydrogenation catalyst to reduce a conjunctpolymer in the spent acidic ionic liquid.

Hydrogenation Catalysts:

In conventional hydrogenation processes, significant quantities ofhydrogenation catalysts are added, along with H₂, to the organiccompounds to be reduced or saturated. The amount of the hydrogenationcatalyst that is required to be added depends to a large extent on themetals present in the hydrogenation catalyst, but typically thehydrogenation catalyst is added in amounts greater than 5 wt % of theorganic compounds being treated. The amount of the metal that needed tobe used in the past for the effective hydrogenation of a spent acidicionic liquid was added in excess to the concentration of the conjunctpolymers present in the spent catalyst. Platinum, palladium, rhodium,and ruthenium can form highly active hydrogenation catalysts, which canoperate at lower temperatures and lower pressures of H₂ compared toother metals. Non-precious metal hydrogenation catalysts, especiallythose based on nickel (such as Raney-nickel and Urushibara-nickel) havealso been developed as economical alternatives, but they are often lessactive and require higher temperatures. The Raney-nickel catalyzedhydrogenations also require high pressures.

Conventional hydrogenation catalysts can comprise at least one metalselected from the group consisting of elements from Group 6 and Groups 8through 10 of the Periodic Table. Hydrogenation catalysts can compriseat least one Group 6 metal and at least one metal selected from Groups 8through 10 of the Periodic Table. For example, the metal can be selectedfrom the group consisting of nickel (Ni), palladium (Pd), platinum (Pt),cobalt (Co), iron (Fe), chromium (Cr), molybdenum (Mo), tungsten (W),and mixtures thereof. Exemplary mixtures of metals that have been usedin hydrogenation catalysts include Ni/Mo/W, Ni/Mo, Ni/W, Co/Mo, Co/W,Co/W/Mo, Ni/Co/W/Mo, and Pt/Pd. Exemplary metal combinations used inhydrogenation catalysts include Ni/Mo/W, Ni/Mo, Ni/W, Co/Mo, Co/W,Co/W/Mo and Ni/Co/W/Mo. Hydrogenation catalysts can be heterogenous orhomogeneous. Heterogenous hydrogenation catalysts are in a differentphase from the unsaturated organic compounds to be reduced or saturated.Typical examples of heterogeneous hydrogenation catalysts involve asolid catalyst with the unsaturated organic compounds being eitherliquids or gases. The unsaturated organic compounds are chemisorbed ontothe heterogeneous hydrogenation catalyst, and hydrogen forms surfacehydrides from which hydrogen can be transferred to the chemisorbedunsaturated organic compounds. Heterogeneous hydrogenation catalysts canbe affected by their supports, i.e. the material upon which theheterogeneous hydrogenation catalyst is bound.

Homogeneous hydrogenation catalysts dissolve in the solvent thatcontains the unsaturated organic compounds to be reduced or saturated.Illustrative homogeneous hydrogenation catalysts include therhodium-based compound known as Wilkinson's catalyst and theiridium-based Crabtree's catalyst.

Unlike earlier known processes used for regenerating acidic ionicliquids by hydrogenation, the process for regenerating a spent acidicionic liquid described herein is done without the addition of ahydrogenation catalyst. Only the spent acidic ionic liquid is contactedwith the hydrogen, and the conjunct polymer is reduced sufficiently toproduce a regenerated acidic ionic liquid.

In one embodiment, no drying or reducing of the spent acidic ionicliquid is done before the contacting.

Contacting Conditions:

The conditions used for the contacting include a temperature less than400° C. (752° F.). In one embodiment, the temperature is from 100° C.(212° F.) to 350° C. (662° F.).

The conditions used for the contacting include sufficient mixing tocontact the spent acidic ionic liquid with hydrogen to produce theregenerated acidic ionic liquid. The sufficient mixing can be done usingany equipment in the vessel that provides effective mixing, such asagitating, baffling, stirring, shaking, bubbling, vortexing, whisking orany other methods (or combinations thereof) known to produce thesufficient mixing. Examples of equipment that can be used to provideeffective mixing include baffles, paddles, agitators, stirrers, nozzles,screens, filters, vibrators, vortex mixers, gas injectors, dispersers,spargers, and combinations thereof. In one embodiment, the contactingoccurs in a vessel with an agitation rate of 50 to 2500 rpm.

The conditions for the contacting include an adequate supply of hydrogento produce the regenerated acidic ionic liquid. In one embodiment, thecontacting occurs in a vessel fed with hydrogen gas and the vesselhaving a pressure greater than 300 kpa. In one embodiment, thecontacting occurs in a vessel under a pressure of 50 to 5000 psig (445to 34600 kpa). Other ranges of pressure in the vessel during thecontacting that can be used include 200 to 4000 psig (1480 to 27700kpa), or 400 to 3000 psig (2860 to 20800 kpa).

The regenerated acidic ionic liquid can be produced over a wide range oftimes, depending on the contacting conditions used. Generally, thecontacting time is greater than 1 hour. In one embodiment, thecontacting time is from 2 to 50 hours.

In one embodiment, paraffinic light gases are formed during thecontacting. These light gases can be entirely non-olefinic, and maycomprise C₂-C₄ alkanes, such as ethane, propane, i-butane, and n-butane.

In one embodiment, an extracted conjunct polymer naphtha having between5 and 30 carbon atoms can be produced by the contacting. In oneembodiment, the extracted conjunct polymer naphtha has a final boilingpoint less than 246° C. (475° F.), a Bromine Number of 5 or less, and atleast 30 wt % naphthenes. In one embodiment, the extracted conjunctpolymer naphtha has at least 60 wt % carbon numbers in a range of C₅through C₁₀. Extracted conjunct polymer naphthas made by contacting aspent acidic ionic liquid and hydrogen with the addition of a solidnoble metal hydrogenation catalyst are disclosed in U.S. Pat. No.8,704,018. In one embodiment, the extracted conjunct polymer naphtha ismixed with an effluent from an alkylation reactor to make a blendedalkylate gasoline.

In one embodiment, no solids are added or formed in a vessel used forthe contacting.

In one embodiment, hydrogen chloride is formed during the contacting.The hydrogen chloride can be dissolved into the spent acidic ionicliquid. In one embodiment, the acidity of the spent acidic ionic liquidcan be modulated by an amount of hydrogen chloride in the vessel usedfor the contacting. In one embodiment, the amount of the hydrogenchloride in the spent acidic ionic liquid is maintained at a level thatincreases a rate of decrease of the content of the conjunct polymer.

Acidic Ionic Liquids:

Acidic ionic liquids can be used as catalysts for various types ofhydrocarbon conversions. Also, the regenerated acidic ionic liquid canalso be effective for catalyzing a hydrocarbon conversion. Examples ofthese hydrocarbon conversions include: an alkylation, a polymerization,a dimerization, an oligomerization, an acylation, a hydrocracking, ametathesis, a copolymerization, an isomerization, a carbonylation, ahydroformylation, a dehalogenation, a dehydration, a disproportionation,a transalkylation, and combinations thereof. In one embodiment, thehydrocarbon conversion is alkylation of paraffins with olefins. Inanother embodiment, the hydrocarbon conversion is alkylation ofaromatics. Examples of ionic liquid catalysts and their use foralkylation of paraffins with olefins are taught, for example, in U.S.Pat. Nos. 7,432,408 and 7,432,409, 7,285,698, and U.S. patentapplication Ser. No. 12/184,069, filed Jul. 31, 2008. In one embodiment,the acidic ionic liquid is a composite ionic liquid catalyst, whereinthe cations come from a hydrohalide of an alkyl-containing amine orpyridine, and the anions are composite coordinate anions coming from twoor more metal compounds. In another embodiment the conversion of ahydrocarbon is alkylation of paraffins, alkylation of aromatics, orcombinations thereof.

The most common acidic ionic liquids are those prepared fromorganic-based cations and inorganic or organic anions. Ionic liquidcatalysts are used in a wide variety of reactions, includingFriedel-Crafts reactions.

The acidic ionic liquid is composed of at least two components whichform a complex. The acidic ionic liquid comprises a first component anda second component. The first component of the acidic ionic liquid willtypically comprise a Lewis acid compound selected from components suchas Lewis acid compounds of Group 13 metals, including aluminum halides,alkyl aluminum dihalides, gallium halide, and alkyl gallium halide (seethe Periodic Table, which defines the elements that are Group 13metals). Other Lewis acid compounds besides those of Group 13 metals mayalso be used. In one embodiment the first component is aluminum halideor alkyl aluminum dihalide. For example, aluminum trichloride (AlCl₃)may be used as the first component for preparing the ionic liquidcatalyst. In one embodiment, the alkyl aluminum dihalides that can beused can have the general formula Al₂X₄R₂, where each X represents ahalogen, selected for example from chlorine and bromine, each Rrepresents a hydrocarbyl group comprising 1 to 12 atoms of carbon,aromatic or aliphatic, with a branched or a linear chain. Examples ofalkyl aluminum dihalides include dichloromethylaluminum,dibromomethylaluminum, dichloroethylaluminum, dibromoethylaluminum,dichloro n-hexylaluminum, dichloroisobutylaluminum, either usedseparately or combined.

The second component making up the acidic ionic liquid is an organicsalt or mixture of salts. These salts may be characterized by thegeneral formula Q⁺A⁻, wherein Q⁺ is an ammonium, phosphonium, boronium,oxonium, iodonium, or sulfonium cation and A⁻ is a negatively chargedion such as Cl⁻, Br⁻, ClO₄ ⁻, NO₃ ⁻, BF₄ ⁻, BCl₄ ⁻, PF₆ ⁻, SbF₆ ⁻, AlCl₄⁻, Al₂Cl₁₇ ⁻, Al₃C₁₀ ⁻, GaCl₄ ⁻, Ga₂Cl₇ ⁻, Ga₃Cl₁₀ ⁻, AsF₆ ⁻, TaF₆ ⁻,CuCl₂ ⁻, FeCl₃ ⁻, AlBr₄ ⁻, Al₂Br₇ ⁻, Al₃Br₁₀ ⁻, SO₃CF₃ ⁻, and3-sulfurtrioxyphenyl. In one embodiment the second component is selectedfrom those having quaternary ammonium halides containing one or morealkyl moieties having from about 1 to about 9 carbon atoms, such as, forexample, trimethylammonium hydrochloride, methyltributylammonium,1-butyl pyridinium, or alkyl substituted imidazolium halides, such asfor example, 1-ethyl-3-methyl-imidazolium chloride.

In one embodiment, the acidic ionic liquid comprises a monovalent cationselected from the group consisting of a pyridinium ion, an imidazoliumion, a pyridazinium ion, a pyrazolium ion, an imidazolinium ion, aimidazolidinium ion, an ammonium ion, a phosphonium ion, and mixturesthereof. Examples of possible cations (Q⁺) include abutylethylimidazolium cation [beim], a butylmethylimidazolium cation[bmim], butyldimethylimidazolium cation [bmmim], decaethylimidazoliumcation [dceim], a decamethylimidazolium cation [dcmim], adiethylimidazolium cation [eeim], dimethylimidazolium cation [mmim], anethyl-2,4-dimethylimidazolium cation [e-2,4-mmim], anethyldimethylimidazolium cation [emmim], an ethylimidazolium cation[eim], an ethylmethylimidazolium [emim] cation, anethylpropylimidazolium cation [epim], an ethoxyethylmethylimidazoliumcation [etO-emim], an ethoxydimethylimidazolium cation [etO-mmim], ahexadecylmethylimidazolium cation [hexadmim], a heptylmethylimidazoliumcation [hpmim], a hexaethylimidazolium cation [hxeim], ahexamethylimidazolium cation [hxmim], a hexadimethylimidazolium cation[hxmmim], a methoxyethylmethylimidazolium cation [meO-emim], amethoxypropylmethylimidazolium cation [meO-prmim], a methylimidazoliumcation [mim], dimethylimidazolium cation [mmim], amethylnonylimidazolium cation [mnim], a methylpropylimidazolium cation[mpim], an octadecylmethylimidazolium cation [octadmim], ahydroxylethylmethylimidazolium cation [OH-emim], ahydroxyloctylmethylimidazolium cation [OH-omim], ahydroxylpropylmethylimidazolium cation [OH-prmim], anoctylmethylimidazolium cation [omim], an octyldimethylimidazolium cation[ommim], a phenylethylmethylimidazolium cation [ph-emim], aphenylmethylimidazolium cation [ph-mim], a phenyldimethylimidazoliumcation [ph-mmim], a pentylmethylimidazolium cation [pnmim], apropylmethylimidazolium cation [prmim], a 1-butyl-2-methylpyridiniumcation[1-b-2-mpy], 1-butyl-3-methylpyridinium cation[1-b-3-mpy], abutylmethylpyridinium [bmpy] cation, a1-butyl-4-dimethylacetylpyridinium cation [1-b-4-DMApy], a1-butyl-4-methylpyridinium cation[1-b-4-mpy], a1-ethyl-2-methylpyridinium cation[1-e-2-mpy], a1-ethyl-3-methylpyridinium cation[1-e-3-mpy], a1-ethyl-4-dimethylacetylpyridinium cation[1-e-4-DMApy], a1-ethyl-4-methylpyridinium cation[1-e-4-mpy], a1-hexyl-4dimethylacetylpyridinium cation[1-hx-4-DMApy], a1-hexyl-4-methylpyridinium cation[1-hx-4-mpy], a1-octyl-3-methylpyridinium cation [1-o-3-mpy], a1-octyl-4-methylpyridinium cation[1-o-4-mpy], a1-propyl-3-methylpyridinium cation[1-pr-3-mpy], a1-propyl-4-methylpyridinium cation[1-pr-4-mpy], a butylpyridinium cation[bpy], an ethylpyridinium cation [epy], a heptylpyridinium cation[hppy], a hexylpyridinium cation [hxpy], a hydroxypropylpyridiniumcation [OH-prpy], an octylpyridinium cation [opy], a pentylpyridiniumcation [pnpy], a propylpyridinium cation [prpy], abutylmethylpyrrolidinium cation [bmpyr], a butylpyrrolidinium cation[bpyr], a hexylmethylpyrrolidinium cation [hxmpyr], a hexylpyrrolidiniumcation [hxpyr], an octylmethylpyrrolidinium cation [ompyr], anoctylpyrrolidinium cation [opyr], a propylmethylpyrrolidinium cation[prmpyr], a butylammonium cation [b-N], a tributylammonium cation[bbb-N], a tetrabutylammonium cation [bbbb-N], abutylethyldimethylammonium cation [bemm-N], a butyltrimethylammoniumcation [bmmm-N], a N,N,N-trimethylethanolammonium cation [choline], anethylammonium cation [e-N], a diethylammonium cation [ee-N], atetraethylammonium cation [eeee-N], a tetraheptylammonium cation[hphphphp-N], a tetrahexylammonium cation [hxhxhxhx-N], a methylammoniumcation [m-N], a dimethylammonium cation [mm-N], a tetramethylammoniumcation [mmmm-N], an ammonium cation [N], a butyldimethylethanolammoniumcation [OHe-bmm-N], a dimethylethanolammonium cation [OHe-mm-N], anethanolammonium cation [OHe—N], an ethyldimethylethanolammonium cation[OHe-emm-N], a tetrapentylammonium cation [pnpnpnpn-N], atetrapropylammonium cation [prprprpr-N], a tetrabutylphosphonium cation[bbbb-P], a tributyloctylphosphonium cation [bbbo-P], or combinationsthereof.

In one embodiment, the second component is selected from those havingquaternary phosphonium halides containing one or more alkyl moietieshaving from 1 to 12 carbon atoms, such as, for example,trialkyphosphonium hydrochloride, tetraalkylphosphonium chlorides, andmethyltrialkyphosphonium halide.

In one embodiment, the acidic ionic liquid comprises an unsubstituted orpartly alkylated ammonium ion.

In one embodiment, the acidic ionic liquid is chloroaluminate or abromoaluminate. In one embodiment the acidic ionic liquid is aquaternary ammonium chloroaluminate ionic liquid having the generalformula RR′R″NH⁺Al₂Cl₇—, wherein R, R′, and R″ are alkyl groupscontaining 1 to 12 carbons. Examples of quaternary ammoniumchloroaluminate ionic liquids are an N-alkyl-pyridinium chloroaluminate,an N-alkyl-alkylpyridinium chloroaluminate, a pyridinium hydrogenchloroaluminate, an alkyl pyridinium hydrogen chloroaluminate, a dialkyl-imidazolium chloroaluminate, a tetra-alkyl-ammoniumchloroaluminate, a tri-alkyl-ammonium hydrogen chloroaluminate, or amixture thereof.

The presence of the first component should give the acidic ionic liquida Lewis or Franklin acidic character. Generally, the greater the moleratio of the first component to the second component, the greater is theacidity of the acidic ionic liquid.

For example, a typical reaction mixture to prepare n-butyl pyridiniumchloroaluminate ionic liquid is shown below:

In one embodiment, the acidic ionic liquid is used as a catalyst for ahydrocarbon conversion and the hydrocarbon conversion utilizes aco-catalyst to provide enhanced or improved catalytic activity. In oneembodiment, the hydrocarbon conversion is alkylating a mixture of one ormore C₄-C₇ isoparaffins and one or more C₂-C₆ olefins in a presence ofan acidic ionic liquid and an alkyl halide or a hydrogen halide toproduce an alkylate gasoline blending component. The alkyl halide or thehydrogen halide can be co-catalysts for the hydrocarbon conversion. Aco-catalyst can comprise, for example, anhydrous HCl or organic chloride(see, e.g., U.S. Pat. No. 7,495,144 to Elomari, and U.S. Pat. No.7,531,707 to Harris et al.) When organic chloride is used as theco-catalyst with the acidic ionic liquid, HCl may be formed in situ inthe apparatus either during the hydrocarbon conversion process or duringpost-processing of the output of the hydrocarbon conversion. In oneembodiment, the hydrocarbon conversion is conducted in the presence of ahydrogen halide, e.g., HCl.

The alkyl halides that may be used include alkyl bromides, alkylchlorides and alkyl iodides. A variety of alkyl halides may be used, butalkyl halide derivatives of the hydrocarbons that comprise the feedstreams to the hydrocarbon conversion (e.g., isoparaffins or the olefinsfor alkylating) can be preferable. Such alkyl halides include but arenot limited to iospentyl halides, isobutyl halides, tertiary butylhalides, n-butyl halides, propyl halides and ethyl halides. Alkylchloride versions of these alkyl halides are preferable whenchloroaluminate ionic liquids are used. Other alkyl chlorides or alkylhalides having from 1 to 8 carbon atoms may be also used. The alkylhalides may be used alone or in combination.

When used, the alkyl halide or hydrogen halide are used in catalyticamounts. In one embodiment, the amounts of the alkyl halides or hydrogenhalide should be kept at low concentrations and not exceed the molarconcentration of the AlCl₃ in the acidic ionic liquid. For example, theamounts of the alkyl halides or hydrogen halide used may range from 0.05mol %-100 mol % of the Lewis acid AlCl₃ in the acidic ionic liquid inorder to keep the acidity of the acidic ionic liquid catalyst at thedesired performing capacity.

Spent Acidic Ionic Liquid:

Spent acidic ionic liquid can be made by using the acidic ionic liquidto perform the hydrocarbon conversion. Over time, the acidic ionicliquid accumulates impurities and becomes less active and selective forperforming the desired hydrocarbon conversion. One of the impuritiesthat accumulates in the acidic ionic liquid is conjunct polymer. Theconjunct polymer deactivates the acidic ionic liquid by weakening theacid strength of the acidic ionic liquid. Complexation of the conjunctpolymer with the acidic ionic liquid can deplete the concentration ofthe Lewis acid in the acidic ionic liquid. As more conjunct polymersaccumulate in the acidic ionic liquid the acidic ionic liquid becomesweaker for performing the desired catalysis. In one embodiment, thespent acidic ionic liquid comprises greater than 3 wt % of the conjunctpolymer. For example, the spent acidic ionic liquid can have fromgreater than 3 wt % to 30 wt % conjunct polymer.

The spent acidic ionic liquid can also comprise corrosion metals. Thecorrosion metals can leach from the metal materials that the acidicionic liquid contacts. Examples of metal materials used for vessels andequipment handling acidic ionic liquids are steel, titanium,nickel-copper alloys, and nickel-based super alloys. Examples of some ofthese metal materials include Inconel® alloys, Incoloy® alloys, Monel®400 alloy, and Hastelloy® alloys. The compositions of some of thesespecific alloys are summarized in Table 1. Inconel® and Incoloy® aretrademarks of Special Metals Corporation.

TABLE 1 Nickel-Copper Alloy Chemical Composition Ranges (all values inweight percent): Alloy UNS # Ni Cu Fe Mn Si S C Monel ® N04400 63.028-34 2.50 2.0 0.024 0.50 0.30 400 min max max max max max Monel ® is atrademark of Special Metals.

TABLE 2 Nickel Based Super Alloy Elemental Composition Ranges (allvalues in weight percent): Hastelloy ® UNS # Ni Cr Mo Fe W Co C-276N10276 Balance 14.5-16.5 15-17 4-7  3-4.5 2.5 max C-22 N06022 Balance 20-22.5 12.5-14.5 2-6 2.5-3.5 2.5 max B2 N10665 Balance 1.0 max 26-302.0 max — 1.0 max Hastelloy ® UNS # Mn C P Si S V C-276 N10276 1.0 max0.01 max 0.04 max 0.08 max 0.03 max 0.35 max C-22 N06022 0.50 max  0.01max 0.02 max 0.08 max 0.02 max 0.35 max B2 N10665 1.0 max 0.02 max 0.04max 0.10 max 0.03 max — Hastelloy ® is a trademark of HaynesInternational, Inc.

In one embodiment, the spent ionic liquid comprises from 100 wppm to50,000 wppm corrosion metals. In one embodiment, the spent ionic liquidcomprises less than 10,000 wppm corrosion metals. In one embodiment, thespent ionic liquid comprises from 10 to 2,500 wppm nickel, wherein thenickel is a corrosion metal.

In one embodiment, the spent acidic ionic liquid catalyst comprises ametal halide. Without being bound by theory, it is possible that ahomogeneous metal halide complex forms in situ in the spent acidic ionicliquid catalyst, and that this complex functions as a homogeneoushydrogenation catalyst. In one embodiment, the homogeneous metal halidecomplex comprises nickel.

Regenerated Acidic Ionic Liquid:

After the contacting, the content of the conjunct polymer in the spentacidic ionic liquid is decreased enough such that the acidic ionicliquid is regenerated. In one embodiment, the content of the conjunctpolymer in the regenerated acidic ionic liquid is 30 wt % to 100 wt % ofthe amount of the conjunct polymer in the spent acidic ionic liquid. Inone embodiment, the conjunct polymer in the regenerated acidic ionicliquid is decreased by at least 50 wt %. In one embodiment theregenerated acidic ionic liquid comprises from 0 to 5 wt % conjunctpolymer. In one embodiment, the regenerated acidic ionic liquidcomprises less than 1.5 wt % of the conjunct polymer.

Feeds for the Hydrocarbon Conversion:

In one embodiment, the feed to the hydrocarbon conversion comprises atleast one olefin and at least one isoparaffin. For example the feed cancomprise a mixture of at least one mostly linear olefin from C₂ to aboutC₃₀. In another embodiment, the feed can comprise at least 50% of asingle alpha olefin species. In one embodiment, the olefin feedcomprises at least one isomerized olefin.

In one embodiment, the feed to an alkylation reactor comprises one ormore C₄-C₇ isoparaffins and one or more C₂-C₆ olefins, and the processproduces an alkylate gasoline blending component.

In one embodiment, the feed to the hydrocarbon conversion comprisesisobutane. Isopentanes, isohexanes, isoheptanes, and other higherisoparaffins up to about C₃₀ are also useable in the process andapparatuses disclosed herein. Mixtures of light isoparaffins can also beused in the present invention. Mixtures such as C₃-C₄, C₃-C₅, or C₄-C₅isoparaffins can also be used and may be advantaged because of reducedseparation costs. The feed to the hydrocarbon conversion can alsocontain diluents such as normal paraffins. This can be a cost savings byreducing the cost of separating isoparaffins from close boilingparaffins. In one embodiment, the normal paraffins will tend to beunreactive diluents in the hydrocarbon conversion.

Reuse of a Previously Used Hydrogenation Vessel:

In one embodiment, a vessel previously containing a solid hydrogenationcatalyst is emptied of the solid hydrogenation catalyst and reused forthe contacting. Even without the solid hydrogenation catalyst in thevessel, the hydrogenation is effective for regenerating the spent acidicionic liquid catalyst.

Apparatus:

In one embodiment, we provide an apparatus that is used for performingthe processes disclosed herein. The apparatus can comprise a vesselcomprising an inlet for introducing the hydrogen, a second inlet forintroducing the spent acidic ionic liquid, equipment that providesmixing of the hydrogen and the spent acidic ionic liquid, a vent, noparts used for separately adding a hydrogenation catalyst, and an outletfor removing the regenerated acidic ionic liquid. In one embodiment, thevessel is a stirred tank reactor where efficient mixing of hydrogen andthe spent acidic ionic liquid catalyst is achieved. In one embodiment,the vessel can comprise an internal particulate filter, having nohydrogenation activity, which provides some or all of the mixing and canbe used for improving dispersion and/or adsorbing any contaminants fromthe spent acidic ionic liquid. Examples of vessels that could use aninternal particulate filter in this manner could include flow-throughopen tubes, plug-flow reactors, or bubble columns. One example of asuitable particulate filter is a Crystaphase CatTrap® internalparticulate filter. In one embodiment, the internal particulate filteris a reticulated ceramic which comes in large discs (1.5″ to 2″diameter). These discs can have the ability to filter and storeparticles inside the discs. Because the large external pathways in thediscs stay open, there is no pressure drop build up as the materialfilters.

EXAMPLES Example 1: Spent Acidic Ionic Liquid Catalyst

A sample of spent acidic ionic liquid catalyst was obtained from analkylation process unit producing alkylate gasoline blending component.The spent acidic ionic liquid catalyst comprised n-butyl pyridiniumchloroaluminate ionic liquid, conjunct polymer, and additional elements.The additional elements included dissolved metals, some as metalhalides. The additional elements were dissolved and were not a colloidalsuspension of solids. The dissolved metals were formed by the corrosionof Monel piping in the alkylation process unit. This sample of spentacidic ionic liquid catalyst had the following properties:

TABLE 3 Spent Acidic Ionic Liquid from Alkylation Reactor ConjunctPolymer Content, wt % 4.10 Elemental Analyses, wppm Chromium 298 Copper3520 Iron 2060 Manganese 158 Nickel 1820 Sulfur 255

The method used to measure the conjunct polymer content was vibrationalinfrared spectroscopy, as described in US Patent Publication No.US20120296145A1.

To perform the elemental analyses the samples were prepared using aMilestone Ethos Plus™ closed vessel microwave digestion system accordingto ASTM D4309-12, “Standard Practice for Sample Digestion Using ClosedVessel Microwave Heating Technique for the Determination of Total Metalsin Water”. The digested solutions were then analyzed by inductivelycoupled plasma-atomic emission spectrometry (ICP-AES) according to ASTMD7260-12, “Standard Practice for Optimization, Calibration, andValidation of Inductively Coupled Plasma-Atomic Emission Spectrometry(ICP-AES) for Elemental Analysis of Petroleum Products and Lubricants”.

The spent acidic ionic liquid catalyst sample was examined under ascanning electron microscope (SEM) using a Mylar sample cell that keptthe spent acidic ionic liquid sample in an anhydrous atmosphere. Using aback scattering technique, the presence of particles containingcorrosion metal elements was searched and no solid metal particlescontaining heavy metals (Ni, Fe, and Cu) were observed.

Example 2: Hydro-Regeneration in the Absence of Added Catalyst and withVessel Drying and Hydrogen Pre-Treatment

An empty 1.2 liter jacketed HASTELLOY® C-22 vessel, equipped with aHASTELLOY C-22 temperature sensor, HASTELLOY C-22 catalyst basket, andHASTELLOY C-22 gassing agitator, were heated to 176.7° C. (350° F.)under a flow of 190 cc/min. of nitrogen and held at that temperature for15 hours to dry the vessel. HASTELLOY is a registered trademark ofHaynes International, Inc. The apparatus used for this example is shownin FIG. 1. The flow of nitrogen was stopped, and hydrogen gas wasintroduced into the vessel at 190 cc/min. The vessel was subsequentlypressurized with hydrogen at 400 psig (2860 kpa) and held at this sametemperature and pressure for seven hours. The vessel was then cooled toroom temperature, depressurized, and hydrogen was purged from the vesselby pressurizing the vessel with nitrogen to 400 psig (2860 kpa),depressurizing, and repeating this pressurization/depressurizationsequence twice.

510 g of the spent acidic ionic liquid catalyst described in Example 1was charged to the vessel by nitrogen pressure transfer from a glassbottle. No catalyst was added to the catalyst basket. The vessel waspurged with nitrogen by pressuring the vessel with nitrogen to 400 psig(2860 kpa), depressurizing, and repeating thispressurization/depressurization sequence twice. About 50 psig (445 kpa)of nitrogen was applied, and the vessel was heated to 180° C. (356° F.)over two hours while agitating at 400 rpm. When the target 180° C. (356°F.) temperature was reached, a sample was taken from the vessel andanalyzed for conjunct polymer content. The conjunct polymer content was4.26 wt %, which was close to the 4.10 wt % in the spent acidic ionicliquid catalyst that was analyzed prior to charging it to the vessel.The agitation was stopped, and hydrogen was exchanged for the nitrogenin the headspace of the vessel by depressurizing the vessel,pressurizing with hydrogen to 400 psig (2860 kpa), depressurizing, andrepeating the pressurization/depressurization cycle twice. The vesselwas then pressurized to a 400 psig (2860 kpa) reaction pressure withhydrogen. The agitator was started at 700 rpm to obtain a well-definedtime for the start of reaction. Reaction progress was monitored twoways: (a) by measuring the hydrogen consumption, calculated from thepressure change of the reservoir feeding the vessel, and (b) byanalyzing samples taken directly from the vessel using vibrationalinfrared spectroscopy.

The data from this run is shown in FIG. 2. The hydrogen consumptionprofile flattened about 20 hours after the start of reaction, and theconjunct polymer content decreased from 4.26 wt % to about 1 wt % overthe same time period. The correlation of the hydrogen consumptionprofile with the decrease in conjunct polymer content showed that thedecrease in the conjunct polymer content occurred due to a combinationof hydrogenation and hydrocracking. Hydrogenations are catalyzed bymetals (see page 4) whereas hydrocracking typically requires abifunctional metal catalyst comprising a hydrogenation function and anacidic function, typically from an acidic support or perhaps an acidicsolvent. One novel and remarkable feature of this example was theoccurrence of hydrogenation and hydrocracking in the complete absence ofany added hydrocracking or hydrogenation catalyst. In theory, thecatalytic hydrogenation activity can be attributed in part to thedissolved corrosion metals, which originated from either corrosion ofMonel piping in the alkylation unit and which were present in aconcentration exceeding 1000 ppm (see Example 1) or from corrosion ofthe Hastelloy vessel wall and inserts.

Example 3: Lab-Prepared Spent Acidic Ionic Liquid

A lab-prepared spent acidic ionic liquid catalyst comprising n-butylpyridinium chloroaluminate ionic liquid, conjunct polymer, and withoutsignificant amounts of additional elements, was prepared as follows. 272g of t-butyl chloride was added to a glass flask containing about 1358 gfresh n-butyl pyridinium chloroaluminate ionic liquid and 100 mln-heptane. The mixture was stirred in the glass flask while immersed inan ice bath for 1.5 hours, then removed from the ice bath and stirredfor an additional hour. The as-prepared reaction product in the glassflask had 6.9 wt % conjunct polymer, and it was diluted with freshn-butyl pyridinium chloroaluminate ionic liquid to a level of 4.4 wt %conjunct polymer. This sample of lab-prepared spent acidic ionic liquidcatalyst had the following properties:

TABLE 4 Lab-Prepared Spent Acidic Ionic Liquid Conjunct Polymer Content,wt % 4.4 Elemental Analyses, wppm Chromium <2.9 Iron <23 Molybdenum <5.7Nickel <2.9 Sulfur <29One key feature of this lab-prepared conjunct polymer was its low metalcontent (<10 wppm), which was in sharp contrast to the spent acidicionic liquid from the alkylation plant (Table 3). This lab-preparedconjunct polymer with a low metal content was well suited to investigatethe impact of dissolved metals on decreasing the content of the conjunctpolymer, or conjunct polymer removal.

Example 4: Hydro-Regeneration in the Absence of Added Catalyst andwithout Vessel Drying and Hydrogen Pre-Treatment

The empty 1.2 liter jacketed HASTELLOY® C-22 vessel described in Example2 was charged with 510 g sample of the lab-prepared spent acidic ionicliquid described in Example 3. No hydrogenation catalyst was added tothe catalyst basket. In this example, vessel drying and hydrogenpre-treatment were not carried out. The lab-prepared spent acidic ionicliquid in the vessel was heated to 180° C. (356° F.) over 1.8 hours, thevessel headspace was exchanged with hydrogen, and the reaction startedas described for Example 2.

The data from this experiment is shown in FIG. 3. Hydrogen consumptionwas again correlated with conjunct polymer decrease, similar to thefindings in Example 2. The conjunct polymer content decreased from 4.4wt % to about 0 wt % (less than detectable) in less than 20 hours ofreaction time. No solids formation occurred in the vessel. This exampledemonstrated that the hydro-regeneration of the spent acidic ionicliquid catalyst was conducted in the absence of an added hydrogenationcatalyst, and even without drying or hydrogen pre-treatment. No solidswere added or formed in the vessel used for the contacting.

More significantly, the decrease in the content of conjunct polymer byhydrogenation/hydrocracking occurred with a much lower level ofcorrosion metals present in the feed. Despite the occurrence of somecorrosion in the vessel (as evidenced, for example, by the increase innickel from 33 wppm at the reaction start to 376 wppm at the reactionend), the conjunct polymer removal occurred even though the corrosionmetals content was more than an order of magnitude lower than inExample 1. The impact of corrosion metals on conjunct polymer removal isevidently weak,

TABLE 5 Metal Leaching in Lab-Prepared Spent Acidic Ionic LiquidCatalyst After Heating, After 22.4 Hours Freshly Before Hydrogen Contactwith Prepared Introduction Hydrogen Conjunct Polymer 4.4 4.9 0 Content,wt % Elemental Analyses, wppm Chromium <2.9 18.4 154.0 Iron <23 44.894.5 Molybdenum <5.7 17.6 64.5 Nickel <2.9 33.3 376.0 Sulfur <29 <25 <21

Example 5: Hydro-Regeneration in the Absence of Added Catalyst, withoutVessel Drying and Hydrogen Pre-Treatment, and with Minimal Exposure toMetal Surfaces

The experiment described in Example 4 was repeated, but with a glasssleeve placed in the vessel to minimize exposure of the spent acidicionic liquid catalyst to metal surfaces. The catalyst basket was removedbefore starting this experiment, and a pitched-blade impeller with asolid shaft was used instead of the hollow shaft gassing agitator usedin Examples 1 and 3. The aforementioned changes decreased the metalsurface area exposed to the ionic liquid by 85%, thus decreasingexposure of metal surfaces to the acidic ionic liquid significantly. Asshown in FIG. 4, the impact of significantly smaller metal exposure tothe acidic ionic liquid did not impact the rate of decrease in contentof the conjunct polymer significantly. As expected, the dissolved metalscontent in the reaction mixture was much lower due to the smaller metalexposure; for example, the nickel content ranged from 17 to 140 wppmover the length of the reaction vs. 33-376 wppm in Example 4.

This example thus indicated that a lower metals content in the acidicionic liquid at the start of reaction had no significant impact on therate of decrease of the conjunct polymer content for the same acidicionic liquid. It indicated further that the impact of corrosion metalsconcentration in the acidic ionic liquid on the rate of decrease of theconjunct polymer content was weak, or negligible.

Example 6: Composition of Headspace Gas

Another regeneration experiment was conducted in a manner similar tothat described in Example 4, but at a 230° C. (446° F.) reactiontemperature. The headspace gas composition was analyzed using an on-linegas chromatograph (GC), connected to the same line as used for the vent.

TABLE 6 GC Analysis of Headspace Gas Component Area % Methane 4.92Ethane 9.24 Propane 30.22 i-Butane 29.06 n-Butane 17.36 i-Pentane 6.71n-Pentane 1.83

The GC analysis of the headspace gas revealed that only alkanes wereformed. While not being bound by theory, the findings that the headspacegas comprised only alkanes and that no olefins were formed wasconsistent with the expected product distribution obtained by catalytichydrocracking. In catalytic hydrocracking, initially formed olefins dueto cracking are thought to be hydrogenated to give paraffins.

Even at the highest temperature used (namely, 230° C.), no lightolefinic components (typically formed in thermal cracking) weredetected.

Example 7: Impact of Pressure on Conjunct Polymer Decrease Rate

The experiment described in Example 2 was repeated at two otheroperating pressures of 200 psig, and 800 psig. The results of theseexperiments were compared to results at 400 psig (Example 1) in FIGS. 4and 5. The data showed a strong impact of pressure on the rate ofdecrease of the conjunct polymer, with the higher reactor pressure or H₂partial pressure causing a significantly higher rate of conjunct polymerremoval. The 800 psig data showed that a 1 wt % level of conjunctpolymer was achieved in about 10 hours at 180° C. (356° F.). Oneadvantage to operating at higher pressures and at a more moderatetemperature is that corrosion rates of the vessel used for thehydrogenation can be lower. The strong impact of the reactor pressureseen in this example was also consistent with the theory that thedecrease in the content of the conjunct polymer in the acidic ionicliquid occurred by hydrogenation and hydrocracking.

Example 8: Impact of Dissolved Hydrogen Chloride in Acidic Ionic Liquid

The apparatus shown in FIG. 1 was modified as indicated in FIG. 7 toallow introduction of hydrogen by a flow-through method, thus allowingfor continuous removal of light components during the reaction. Aprocedure similar to that given in Examples 2, 4, 5, and 7 was used,except that hydrogen gas was introduced via a mass flow controller andthe reactor pressure was controlled using a back-pressure regulator.Hydrogen chloride content in the offgas was monitored by measuring thepH of the absorbing water solution as a function of time using a pHprobe immersed in this solution.

As conversion of conjunct polymer is known to produce hydrogen chloride,which could impact the acidic character of acidic ionic liquid, it wasdesired to evaluate the impact of hydrogen chloride on conjunct polymerremoval. The data in FIG. 8 compared this Example 8 experiment with thatfrom Example 2 and indicated that the decrease in the content of theconjunct polymer in the acidic ionic liquid was slower when hydrogenchloride was continuously removed from the reaction mixture.

This example indicated that modulation of the acidity of the acidicionic liquid by dissolved hydrogen chloride can be an importantparameter in conjunct polymer removal in the absence of ahydrogenation/hydrocracking catalyst.

Our examples above have shown that the conjunct polymer content in aspent acidic ionic liquid catalyst can be decreased effectively byhydrogenating and hydrocracking in the complete absence of a solidhydrogenation catalyst. In the absence of a solid hydrogenationcatalyst, the conjunct polymer was hydrocracked to lighter moleculesthat were fully saturated. The reactor pressure and/or H₂ partialpressure of the reactor, and dissolved HCl content in the acidic ionicliquid, were both important factors affecting the rate of decrease(hydrocracking reaction rate) of the conjunct polymer. While we do notwant to be bound by theory, it appears that the acidic functionality toperform the hydrocracking came from the acidic ionic liquid. Uponhydrocracking of the conjunct polymer, olefinic reaction intermediateswere created. The olefinic reaction intermediates were hydrogenated withthe H₂ gas present in the reactor. The source of the hydrogenationfunctionality in this catalytic reaction was not clear, but appeared tobe related to the acidic ionic liquid (organo-aluminum halide) and thehydrogen chloride. The dissolved corrosion metals in the acidic ionicliquids may have contributed to the hydrogenation and production offully saturated light hydrocarbons, however the contribution of thesedissolved corrosion metals was not significant.

The transitional term “comprising”, which is synonymous with“including,” “containing,” or “characterized by,” is inclusive oropen-ended and does not exclude additional, unrecited elements or methodsteps. The transitional phrase “consisting of” excludes any element,step, or ingredient not specified in the claim. The transitional phrase“consisting essentially of” limits the scope of a claim to the specifiedmaterials or steps “and those that do not materially affect the basicand novel characteristic(s)” of the claimed invention.

For the purposes of this specification and appended claims, unlessotherwise indicated, all numbers expressing quantities, percentages orproportions, and other numerical values used in the specification andclaims, are to be understood as being modified in all instances by theterm “about.” Furthermore, all ranges disclosed herein are inclusive ofthe endpoints and are independently combinable. Whenever a numericalrange with a lower limit and an upper limit are disclosed, any numberfalling within the range is also specifically disclosed. Unlessotherwise specified, all percentages are in weight percent.

Any term, abbreviation or shorthand not defined is understood to havethe ordinary meaning used by a person skilled in the art at the time theapplication is filed. The singular forms “a,” “an,” and “the,” includeplural references unless expressly and unequivocally limited to oneinstance.

All of the publications, patents and patent applications cited in thisapplication are herein incorporated by reference in their entirety tothe same extent as if the disclosure of each individual publication,patent application or patent was specifically and individually indicatedto be incorporated by reference in its entirety.

This written description uses examples to disclose the invention,including the best mode, and also to enable any person skilled in theart to make and use the invention. Many modifications of the exemplaryembodiments of the invention disclosed above will readily occur to thoseskilled in the art. Accordingly, the invention is to be construed asincluding all structure and methods that fall within the scope of theappended claims. Unless otherwise specified, the recitation of a genusof elements, materials or other components, from which an individualcomponent or mixture of components can be selected, is intended toinclude all possible sub-generic combinations of the listed componentsand mixtures thereof.

The invention illustratively disclosed herein suitably may be practicedin the absence of any element which is not specifically disclosedherein.

It is claimed:
 1. An apparatus for regenerating a spent acidic ionicliquid, comprising a vessel comprising an inlet for introducing ahydrogen, a second inlet on the vessel for introducing the spent acidicionic liquid, an equipment in the vessel that provides mixing of thehydrogen and the spent acidic ionic liquid, a vent on the vessel, noparts for separately adding a hydrogenation catalyst to the vessel, andan outlet on the vessel for removing a regenerated acidic ionic liquid;wherein the apparatus is used for performing a process for regeneratingthe spent acidic ionic liquid, the process comprising contacting thespent acidic ionic liquid in the vessel used for the contacting with thehydrogen and without an addition of the hydrogenation catalyst; whereina content of a conjunct polymer is decreased in the spent acidic ionicliquid to produce the regenerated acidic ionic liquid; additionallycomprising an internal particulate filter, in the vessel, having nohydrogenation activity, wherein the internal particulate filter is areticulated ceramic disc having a diameter from 1.5 to 2 inches (3.81 to5.08 centimeters).
 2. The apparatus of claim 1, wherein the vesselcomprises a flow-through open tube.
 3. The apparatus of claim 1, whereinthe vessel comprises a plug-flow reactor.
 4. The apparatus of claim 1,wherein the vessel comprises a bubble column.
 5. The apparatus of claim1, wherein the internal particulate filter provides some of the mixingof the hydrogen and the spent acidic ionic liquid.
 6. The apparatus ofclaim 1, wherein the internal particulate filter provides all of themixing of the hydrogen and the spent acidic ionic liquid.
 7. Theapparatus of claim 1, wherein the internal particulate filter hasexternal pathways that stay open as a material in the reticulatedceramic disc filters and stores particles inside the reticulated ceramicdisc.
 8. The apparatus of claim 1, wherein the vessel is a stirred tankreactor.
 9. The apparatus of claim 1, additionally comprising aback-pressure regulator, connected to the vessel, that maintains anamount of a hydrogen chloride in the spent acidic ionic liquid in thevessel at a level that increases a rate of decrease of the content ofthe conjunct polymer.
 10. The apparatus of claim 1, wherein the vesselis an emptied vessel, that had previously contained a solidhydrogenation catalyst, that is reused in the apparatus.
 11. Theapparatus of claim 1, wherein the vessel is a nickel-based super alloyvessel.
 12. The apparatus of claim 1, wherein the equipment in thevessel comprises a gassing agitator.